Interfacing electron-rich metal nanoparticles with graphene derivatives can sensitively regulate the properties of the resultant hybrid with potential applications in metal-doped graphene field-effect transistors (FETs), surface-enhanced Raman spectroscopy, and catalysis. Here, we show that by controlling the rate of diffusion and catalytic reduction of gold ions on graphene oxide (GO), dendritic "snowflake-shaped" gold nanostructures (SFGNs) can be templated on graphene. The structural features of the SFGNs and their interfacing mechanism with GO were characterized by microscopic analysis and Raman-scattering. We demonstrate that (a) SFGNs grow on GO-surface via diffusion limited aggregation; (b) SFGN's morphology (dendritic to globular), size (diameter of 150-500 nm and a height of 45-55 nm), coverage density, and dispersion stability can be controlled by regulating the chemiophysical forces; (c) SFGNs enhance the Raman signal by 2.5 folds; and (d) SFGNs act as antireduction resist during GO-SFGN's chemical reduction. Further, the SFGNs interfacing with graphene reduces the apparent band gap (from 320 to 173 meV) and the Schottky barrier height (from 126 to 56 meV) of the corresponding FET.
This work addresses a major challenge in liquid-phase catalysis by enabling the synthesis of solvent dispersible "uncapped" metal nanoparticles (NPs) with enhanced density of accessible catalytic sites. We demonstrate that graphene oxide's (GO's) high density of accessible and bondable oxy-functional groups and the high steric hindrance from its micrometer-scale area covalently implant, stabilize, and support bare-surfaced gold nanoparticles (BSGNs) produced in situ by a unique microwave reduction process. Comparing the efficiency of catalytic reduction of p-nitroaniline ( p-NA) by BSGNs and similar sized surfactant-capped gold NPs showed that the uncapped surface on GO-supported NPs, (a) opens up 258% more active sites, and (b) enhances the catalytic reduction of p-NA by 10-100 fold. Further, BSGN implantation on GO, (a) amplifies the Raman signal of bare GO by ∼3 fold, and (b) increases the conductivity of native p-type GO by >10 fold via injection of 1.328 Â 10 12 electrons/cm 2 , consequently transforming it into an n-type semiconductor.
The discovery of graphene has led to a rising interest in seeking quasi two-dimensional allotropes of several elements and inorganic compounds. Boron, carbon’s neighbour in the periodic table, presents a curious case in its ability to be structured as graphene. Although it cannot independently constitute a honeycomb planar structure, it forms a graphenic arrangement in association with electron-donor elements. This is exemplified in magnesium diboride (MgB2): an inorganic layered compound comprising boron honeycomb planes alternated by Mg atoms. Till date, MgB2 has been primarily researched for its superconducting properties; it hasn’t been explored for the possibility of its exfoliation. Here we show that ultrasonication of MgB2 in water results in its exfoliation to yield few-layer-thick Mg-deficient hydroxyl-functionalized nanosheets. The hydroxyl groups enable an electrostatically stabilized aqueous dispersion and create a heterogeneity leading to an excitation wavelength dependent photoluminescence. These chemically modified MgB2 nanosheets exhibit an extremely small absorption coefficient of 2.9 ml mg−1 cm−1 compared to graphene and its analogs. This ability to exfoliate MgB2 to yield nanosheets with a chemically modified lattice and properties distinct from the parent material presents a fundamentally new perspective to the science of MgB2 and forms a first foundational step towards exfoliating metal borides.
Two-dimensional (2D) metal-boride-derived nanostructures have been a focus of intense research for the past decade, with an emphasis on new synthetic approaches, as well as on the exploration of possible applications in next-generation advanced materials and devices. Their unusual mechanical, electronic, optical, and chemical properties, arising from low dimensionality, present a new paradigm to the science of metal borides that has traditionally focused on their bulk properties. This Perspective discusses the current state of research on metalboride-derived 2D nanostructures, highlights challenges that must be overcome, and identifies future opportunities to fully utilize their potential.
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